3,7-Dioxaazelaamides as Ionophores for Lithium Ion Selective Liquid Membrane Electrodes

Lipophilic neutral carriers were synthesized which show Li⁺/Na⁺ selectivities of up to ca. 80 in highly lipophilic liquid membranes. The sensor membranes exhibit improved response times and increased lifetimes as compared to systems described earlier. They allow reliable measurements of Li⁺ in blood serum within the clinical concentration range. A 1:1 Li⁺/ionophore complex of one representative (N,N,N′,N′-tetracyclohexyl-5,5-dimethyl-3,7-dioxaazelaamide) has been prepared, and its structure was elucidated by X-ray analysis.     

Radical cyclization cascade involving ynamides: an original access to nitrogen-containing heterocycles

A radical cascade involving a 5-exo-dig cyclization followed by a 6-endo-trig radical trapping transforms ynamides into heterogeneous polycyclic compounds in good yields. This leads interestingly to the formation of isoindols, isoindolinones, and pyridoisoindolones. [reaction: see text]     

Improved separation of palladium species in biological matrices by using a combination of gel permeation chromatography and isotachophoresis

The binding of palladium to high-molecular-mass compounds in palladium-treated lettuce is investigated as an example for a biological matrix. The total palladium concentration in lettuce leaves is 10.3 ng/g wet weight. After homogenization, high-molecular-mass compounds (> 10 kDa) are isolated by ultrafiltration. For separation of these palladium species a combination of preparative gel permeation chromatography (GPC) and preparative isotachophoresis (ITP) is used. Palladium is determined in separated fractions by using a highly sensitive total reflection X-ray fluorescence (TXRF) method after preconcentration. After GPC separation, four main fractions of palladium species are collected, each containing palladium in ng quantities (3-10 ng). Two of these fractions are further separated by ITP, yielding at least three main peaks per GPC fraction, each containing palladium in the range of 0.3-3 ng. These palladium containing peaks are characterized by high-performance size exclusion chromatography (HPSEC) and capillary isotachophoresis (cITP) in parallel. HPSEC enables the estimation of the molecular mass of six main palladium peaks, covering a molecular mass range of 69-200 kDa. It is also shown that the estimation of molecular mass after separation is more reliable than the respective estimation directly in the first GPC run. However, cITP reveals that each of the separated peaks is still a mixture of at least five different compounds.     

Etorphine‐Related Ferrocenyl‐Substituted Morphinan Alkaloids

The two diastereoisomeric ferrocenyl‐substituted orvinols 2 and 3 were prepared. The modified alkaloids are still able to interact with opioid receptors (see Table). The ferrocene moiety allows highly selective and sensitive electrochemical detection. The X‐ray crystal structure of the major isomer 2 was determined. The combination of a metallocene and a morphinan alkaloid holds promise for useful antitumor activity.     

Thermal conductivity and specific heat of amorphous Zr0.67Ni0.33 after structural relaxation

Low-temperature measurements of the thermal conductivity (0.3KT5K) and of the specific heatC (0.07KT3.5K) of splat-cooled amorphous superconducting Zr_0.67Ni_0.33(T _c 2.7K) after different annealing stages are reported. increases progressively (up to 55%) after annealing. An analysis of with the help of normal-state measurements belowT _c in an overcritical field shows that the phonon-electron scattering remains unaltered after annealing. Hence the increase in must be entirely attributed to structure-induced (intrinsic) scattering, i.e. by two-level tunneling states (TLS) at low temperatures (T1K). The specific heat shows a small decrease aboveT _c (by 8%) which is attributed to a small diminution of the electronic density of states at the Fermi level and to a small increase in the Debye temperature. ForTT _c where TLS dominate, the specific heatC decreases less upon annealing than expected from the increase of in the standard tunneling model. This points to a change in the TLS relaxation time spectrum upon annealing, as observed previously for Zr _x Cu_1–x glasses.     

Rotational-diffusion anomalies in dye solutions from transient-dichroism experiments

Subnanosecond transient-dichroism experiments have been performed to investigate the rotational diffusion of dyes in solution. Dyes and solvents were chosen in a way to obtain information on the influence of size, shape and hydrogen-bonding abilities either of the solute or the solvent molecules. One finds slow orientational relaxation of di-anionic xanthene dyes in alcohols, while oblate cationic dyes rotate faster in spite of their comparable size. The rotational diffusion times for alcohol solutions exceed the theoretical values predicted by the Debye-Einstein model except for prolate molecules. For a solute molecule with internal mobility the rotational diffusion exhibits a partial slip behaviour. It is shown that the deviations from the Debye-Einstein model are restricted to alcohols since for other solvents either with or without strong hydrogen-bonding abilities the experimental values agree with the hydrodynamic model including the stick-boundary condition. Experiments on erythrosine B reveal the influence of size and shape of the attached solvent molecules.     

Direct measurement of gas solubility and diffusivity in poly(vinylidene fluoride) with a high-pressure microbalance

We present solubility and diffusion data for the gases methane and carbon dioxide in the polymer poly(vinylidene fluoride). The polymer was cut from extruded piping intended for use in offshore oil and gas applications. Measurements were carried out using a purpose-built high-pressure microbalance. These properties were determined in the temperature range 80-120 °C and in the pressure range 50-150 bar for methane and 20-40 bar for carbon dioxide. In general, good agreement was obtained for similar measurements reported in the literature. Solubility follows a Henry’s law (linear) dependence with pressure. Diffusion coefficients for each of the gases in the polymer were also measured using the balance. Activation energies for diffusion and heats of solution for the two gases in the polymer were also determined.     

Über Pterinchemie. 49. Mitteilung. Eine neue Synthese von 5-Formyl-6, 7-dimethyl-5,6,7,8-tetrahydropterin und 5,6,7-Trimethyl-5,6,7,8-tetrahydropterin

Starting with 5-formyl-6,7-dimethyl-5,6,7,8-tetrahydropterine (II), a new synthesis of 5,6,7-trimethyl-5,6,7,8-tetrahydropterine (III) is described. Thereby the chemical behaviour of the 5-formyl group in II is investigated, in order to enable the unequivocal differentiation between formylation at position 5 and at position 10 in folic and tetrahydrofolic acid derivatives. ¹³C-NMR. spectra of II and III are discussed.